KR101742295B1 - Calcium removal method from hydrocarbon fractions using extraction comprising 2-oxopropanal or derivatives thereof - Google Patents

Abstract

The present invention relates to a method for removing calcium in a hydrocarbon oil, and more particularly, to a method for removing calcium in a hydrocarbon oil by using an extracting agent comprising 2-oxopropanal or a derivative thereof ≪ / RTI > A method for removing calcium in a hydrocarbon oil for this purpose includes a first step of adding an extraction agent containing 2-oxopropanal or a derivative thereof to a hydrocarbon oil to prepare a mixture; A second step of reacting 2-oxopropanal or a derivative thereof with a hydrocarbon oil to convert the fat-soluble calcium compound into a water-soluble calcium compound; And a third step of removing the water-soluble calcium compound.

Description

[0001] CALCIUM REMOVAL METHOD FROM HYDROCARBON FRACTIONS USING EXTRACTION COMPRISING 2-OXOPROPANAL OR DERIVATIVES THEREOF [0002] BACKGROUND OF THE INVENTION [0003] The present invention relates to a method for removing calcium from a hydrocarbon oil using an extracting agent comprising 2-oxopropanal or a derivative thereof.

The present invention relates to a method for removing calcium in a hydrocarbon oil, and more particularly, to a method for removing calcium in a hydrocarbon oil by using an extracting agent comprising 2-oxopropanal or a derivative thereof ≪ / RTI >

On the land and sea, heavy oil fields containing metal impurities such as calcium are distributed. Particularly, in the marine oil field containing a large amount of organic acid, the organic acid contained in the oil in the production process is combined with the salt contained in the water injected for the oil production, particularly, calcium to form organic calcium, There is also a case where the content of calcium contained in the oil is increased.

In this case, it was excluded from the development due to low economic efficiency in the past, but recently it has become known that impurity treatment can secure higher refining margins or sales margins, It is actually participating in development. Typical high-calcium oil fields include Doba and Kuito in West Africa and Heidrum and Captain in the North Sea. In Asia, there are Bohai Bay and Shengli in China and Serang in Indonesia. As you can see from these examples, these high calcium heritages are found all over the world.

In the case of general crude oil, calcium is often present as a salt such as CaCl ₂ and is easily removed through a desalting process. However, in the case of oil from oil fields, calcium is often combined with organic acids such as naphthenic acid to form calcium taxaneate. Calcium naphthenate (CaNA) refers to the combination of anion and calcium cation of naphthenic acid, and it is important that the chemical structure of naphthenic acid anions is very diverse. It is almost impossible to treat calcium tansate because it enhances the stability of the emulsion produced in the desalting process because it has both hydrophilicity and hydrophobicity.

On the other hand, calcium contained in crude oil causes the following problems in each process of refinery process.

1) Tank Farm - High BS & W (Basic sediment and water)

2) Desalting - emulsion level control, voltage reduction due to high conductivity of calcium (Ca)

3) Waste Water Treatment - Water Carryover, Poor Effluent Water Quality

4) Heat exchanger and preheater - Calcium deposits and degradation of heat exchange efficiency

5) Fluid Catalytic Cracking Unit (FCCU) or Residual Fluid Catalytic Cracking Unit (RFCCU)

6) High calcium content of coke and heavy fuel oil

Due to these problems, high-calcium crude oil, which has a high calcium content, is being traded at a lower price than general light oil. In the refining industry, the high-calcium crude oil is partially diluted with high-quality light oil.

Recently, as a method of removing calcium from crude oil, a method of removing calcium from calcium taxaneate using acidic compounds such as sulfuric acid, carboxylic acid ester, water-soluble hydroxy acid, and maleic acid has been studied.

According to U.S. Patent No. 5,593,573, sulfuric acid or a salt thereof is used as a calcium scavenger. In this case, there is a problem that an excessive amount of a precipitation inhibitor must be added in order to prevent calcium sulfate from being rapidly formed in the desalting process.

Korean Patent Registration No. 10-1340718 discloses a method for removing calcium from hydrocarbon oil using maleic acid or a derivative thereof. However, when this method is applied to crude oil or a hydrocarbon oil containing water, Which is known to show a problem of rising up toward the crude oil and hydrocarbon oil.

Thus, there is a need for a method for effectively removing calcium in hydrocarbon oils such as crude oil.

U.S. Patent No. 5,593,573 Korean Registered Patent No. 10-1340718

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a method of effectively removing calcium in a hydrocarbon oil using an extracting agent comprising 2-oxopropanal or a derivative thereof .

These and other objects and advantages of the present invention will become apparent from the following description of a preferred embodiment.

The object is achieved by a process comprising the steps of: (1) preparing an admixture by adding an extracting agent comprising 2-oxopropanal or a derivative thereof to a hydrocarbon oil fraction; A second step of reacting 2-oxopropanal or a derivative thereof with a hydrocarbon oil to convert the fat-soluble calcium compound into a water-soluble calcium compound; And a third step of removing the water-soluble calcium compound.

In the first step, the extractant may be added in an amount of 0.1 to 100 times (based on the molar ratio) of the calcium content contained in the hydrocarbon oil, and the extractant may be added in a solid phase or in a mixed solution in which water or an organic solvent is dissolved have. When the extractant is added as a solid phase, it can be stirred at 0 to 350 ° C to form a homogeneous mixture. When the extractant is added in the form of a mixture of water and an organic solvent, the mixture is stirred at 0 to 350 ° C Stirring can be carried out.

The second step may be carried out at 0 to 350 占 폚.

In the third step, water-soluble calcium compounds can be removed by gravity, and water-soluble calcium compounds can be removed using centrifugal force based on centrifugal force, The water-soluble calcium compound can be removed by using electric desalting or electric coalescence.

In addition, the hydrocarbon oil can be used as crude oil (Crude Oil), Bio oil, Bio diesel, Tight Oil, Shale Oil, Oil Sand, , A tar sand, an atmosphere residue (AR), a vacuum residue (VR), a vapor residue (VR), and a hydrocarbon residue.

Industrial Applicability According to the present invention, it is possible to efficiently remove the calcium component (organic metal form) from a hydrocarbon oil fraction containing a large amount of calcium.

Concretely, it is possible to achieve high value addition of the hydrocarbon oil containing a large amount of calcium, solve the problems of the prior art (use of excessive precipitation inhibitor), improve the efficiency of the calcium removal process and improve the economical efficiency and energy efficiency .

In addition, it can be applied to various facilities such as refinery facilities including desalination and dehydration processes, and onshore and offshore facilities related to hydrocarbon oil.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.

1 is a schematic view illustrating a method of removing calcium in a hydrocarbon oil according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings of the present invention. It will be apparent to those skilled in the art that these embodiments are provided by way of illustration only for the purpose of more particularly illustrating the present invention and that the scope of the present invention is not limited by these embodiments .

Also, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains and, where contradictory, Will be given priority.

In order to clearly illustrate the claimed invention, parts not related to the description are omitted, and like reference numerals are used for like parts throughout the specification. And, when a section is referred to as "including " an element, it does not exclude other elements unless specifically stated to the contrary. In addition, "part" described in the specification means one unit or block performing a specific function.

In each step, the identification code (first, second, etc.) is used for convenience of explanation, the identification code does not describe the order of each step, and each step does not explicitly list a specific order in the context May be performed differently from the above-described sequence. That is, each of the steps may be performed in the same order as described, or may be performed substantially concurrently or in the reverse order.

1 is a schematic view illustrating a method of removing calcium in a hydrocarbon oil according to an embodiment of the present invention. Referring to FIG. 1, a method for removing calcium in a hydrocarbon oil according to an embodiment of the present invention comprises adding an extracting agent containing 2-oxopropanal or a derivative thereof to a hydrocarbon oil fraction A first step of preparing a mixture; A second step of reacting 2-oxopropanal or a derivative thereof with a hydrocarbon oil to convert the fat-soluble calcium compound into a water-soluble calcium compound; And a third step of removing the water-soluble calcium compound.

The extracting agent of the present invention may contain only 2-oxopropanal or a derivative thereof, but may be used in combination with various existing calcium extracting agents as needed. Examples of various conventional calcium extracting agents include Citric acid, HCl, Oxalic acid, NH ₄ OH, Acetic acid, Sulfuric acid, Maleic anhydride, Fumaric acid, Maleic acid, tartaric acid, succinic acid, glycolic acid, and gluconic acid. However, it is not preferable to use an acid-based extracting agent in the case of using a natural separation method by gravity to remove the water-soluble calcium compound in the third step to be described later. This is because the acid-based extracting agent improves emulsion stability, which makes water separation difficult and adversely affects calcium removal.

The present invention can efficiently remove calcium from hydrocarbon oil fractions by using an extraction agent comprising 2-oxopropanal or a derivative thereof. Specifically, an extractant containing 2-oxopropanal or a derivative thereof is superior in stability to an acid-based extractant (sulfuric acid, maleic acid, etc.) or glyoxal that has been used in the past, As can be seen from the examples described later, the calcium removal efficiency from the hydrocarbon oil is excellent.

2-oxopropanal is produced as a by-product of several metabolic pathways in organisms. Specifically, it may be produced from 3-aminoacetone, which is an intermediate of threonine catabolism as well as lipid peroxidation, but is mainly produced by glycolysis. That is, it is produced by nonenzymatic phosphate elimination from glyceraldehydes phosphate and dihydroxyacetone phosphate, two intermediates of glycolysis. (The starting material is different) from the glyoxal produced by liquid-phase oxidation of acetaldehyde in the presence of nitric acid or gas-phase oxidation of ethylene glycol under silver or copper catalysts . In addition, glyoxal reacts with oil due to its high reactivity and is toxic, while 2-oxopropanal is less harmful than glyoxal.

In addition, hydrocarbon oil refers to an oil that is mainly composed of carbon and hydrogen, and does not mix with water. That is, the hydrocarbon oil is used as a raw material of the oil such as bio oil, bio diesel, Tight oil, Unconventional oil, shale oil, oil sands (AR), Atmosphere residue (VR), Vacuum residue (VR), and Residue (VR) that can be extracted from oil sand, liquefied coal oil, tar sand, crude oil refinery or down- Hydrocarbon residue, refinery and petrochemical product groups.

In one embodiment, the first step is to add an extraction agent comprising 2-oxopropanal or a derivative thereof to the hydrocarbon oil fraction to prepare a mixture. At this time, the extractant containing 2-oxopropanal or a derivative thereof is preferably added in an amount of 0.1 to 100 times (based on the molar ratio) of the calcium content in the hydrocarbon oil, more preferably 0.1 to 10 times . When the added amount of 2-oxopropanal or its derivative is less than 0.1 times the calcium content, the calcium removal effect is insufficient because the residual amount of calcium is too low, and when it is more than 100 times, the removal efficiency is not improved any more It is not economical.

Further, the extracting agent containing 2-oxopropanal or a derivative thereof may be added in the form of a solid in the form of a mixed liquid in which the hydrocarbon oil is added in solid phase or dissolved in water or an organic solvent. The present invention can be largely applied to a refinery process for processing high calcium hydrocarbons oil production process (land or marine facility producing oil of high calcium crude oil) and high calcium hydrocarbon oil fraction. The ratio of water in the oil from the oil well can be up to 1 wt.% And finally up to 99 wt.%. In case of refinery process, 0.5 wt.% Or more of water is added to the crude oil coming from the tank farm. Of water. Therefore, even if the extractant containing 2-oxopropanal or its derivative is directly put into the solid phase, it can be dissolved by the moisture contained in the crude oil itself. However, in order to control the concentration of 2-oxopropanal or its derivative in the extractant used, it is dissolved in water, an organic solvent or a demulsifier in advance and then mixed with crude oil or hydrocarbon oil It is also possible to do.

First, when an extractant containing 2-oxopropanal or a derivative thereof is directly added to a hydrocarbon oil fraction in a solid phase, it is preferable to prepare a homogeneous mixture. To provide such a homogeneous mixture, it can be carried out using any known method and can be stirred in a temperature range from 0 to 350 ° C, preferably from 10 to 250 ° C. The stirring time may be several seconds to several hours, preferably 10 seconds to 1 hour. As described above, the extractant component is dissolved by the water present in the hydrocarbon oil and the like. In the case of the hydrocarbon oil having no or relatively little water, water, an organic solvent or a demulsifier may be additionally added. At this time, the concentration of the extractant can be appropriately diluted within the range of 1 to 99%, and it is also important to uniformly mix the extractant in this case.

Next, when an extractant containing 2-oxopropanal or a derivative thereof is added in the form of a mixed solution obtained by dissolving the extractant in water, an organic solvent, or a water-dispersing agent, Or a water-dispersing agent (demulsifier). Can be carried out using any known mixing method for uniform mixing and can be carried out in a temperature range from 0 to 350 ° C, preferably from 10 to 250 ° C, more preferably from 10 to 170 ° C It can be stirred in a temperature range. The stirring time may be 10 seconds to 1 day, preferably 10 seconds to 1 hour, and the homogeneously mixed homogeneous mixed solution is prepared by stirring the mixed solution so that the added extractant is completely dispersed and sufficiently dissolved . Here, the organic solvent may be selected from the group consisting of alcohols (monohydric or polyhydric alcohols), acetone, ketones, esters, glycol, ether / ester, ) And the like.

In one embodiment, the second step is a step of performing a chemical reaction with an extractant comprising a 2-oxopropanal or a derivative thereof and a hydrocarbon oil, wherein the 2-oxopropanal, Or a derivative thereof with a hydrocarbon oil to convert a fat-soluble calcium compound such as calcium persenate into a water-soluble calcium compound such as calcium ion or calcium salt. At this time, in the third step, water or an organic solvent may be additionally supplied so that the water-soluble calcium ion or the calcium salt can be effectively removed.

Particularly, in the second step, it is important to stir the hydrocarbon oil having high viscosity so that the chemical reaction can proceed smoothly with the extractant so that the hydrocarbon oil can be completely mixed in the reactor. Particularly in the case of a continuous process, a mixing pump or a centrifugal pump having a much better mixing ability can be used, so that the mixing ratio may be higher than in a conventional batch process. Also, the reaction is preferably carried out in a temperature range of 0 to 350 ° C. so that the chemical reaction can proceed smoothly in the reactor. The reaction time can be in the range of several seconds to several hours, but the reaction time of 1 minute to 1 hour .

In one embodiment, the third step is to remove the water-soluble calcium compound such as calcium ion or calcium salt formed by the second step. Water-soluble calcium compounds can be removed through a variety of methods, such as natural separation and removal using gravity, centrifugal separation and removal using centrifugal force based on density differences, Separation and removal using electric desalting or electric coalescence may be applied.

Further, in the step of removing the water-soluble calcium compound, a demulsifier may be added to further improve the removal efficiency. The demulsifier may contain polyols, polyamines, amines and the like. The content of the demulsifier may be adjusted by adding the whole mixture (such as an extractant to the hydrocarbon oil) And preferably from 10 to 100 ppm, based on the total weight of the composition. When the amount is less than 1 ppm, the use amount is too small, and the effect is insignificant. When the amount exceeds 10000 ppm, the degree of improvement of the removal efficiency is insignificant, which is uneconomical.

The method of removing water-soluble calcium compounds by gravity (natural separation) is a method of removing by gravity and density difference based on difference in specific gravity between aqueous phase and oil phase. A separator may be used. Specifically, in the temperature range of 10 to 350 占 폚, the ratio of water during the residence time of several minutes to several hours can be performed in the range of 0.5 to 99 wt% of the entire mixture.

The method of removing water-soluble calcium compounds by centrifugation (centrifugation) can be carried out in the range of g-force in the range of 10 to 1000 on the ASTM basis. Specifically, it can be carried out in the range of 100 to 15000 rpm, preferably 500 to 10000 rpm, for several minutes to 48 hours, preferably 10 minutes to 24 hours. The temperature range is preferably 10 to 350 占 폚.

The electrolytic desalting method using electrodialysis method or the method of removing water-soluble calcium compound using electrical fusing (electrodeposition method) can be carried out using a conventional electrodemulsion apparatus. The voltage may be a direct current or an alternating current of 100 to 10,000 V / cm and may be carried out at a temperature of 10 to 350 DEG C for 5 minutes to 3 hours, preferably 5 minutes to 1 hour. In this case, the proportion of water used may be 0.01 to 50 wt%, preferably 0.01 to 20 wt% of the total mixture. As additional additives, a demulsifier may be used in an amount of 1 to 100 ppm, preferably 2 to 50 ppm, based on the total mixture.

Hereinafter, the structure and effect of the present invention will be described in more detail with reference to examples and comparative examples. However, this embodiment is intended to explain the present invention more specifically, and the scope of the present invention is not limited to these embodiments.

[Experimental Example]

(Centrifugation, natural separation, electrodeposition) was carried out using 2-oxopropanal and various calcium extractants to remove calcium from calcium-containing crude oil (high calcium crude oil) Contains 100 ppm of calcium. The calcium removal rate refers to the removal efficiency calculated from the following equation (1) by measuring the concentration (C _{Ca 0} ) before the calcium removal experiment and the concentration after the experiment (C _Ca ) of the crude oil sample.

(1)

_{(C Ca, 0 -C Ca)} / C Ca, 0 x 100

[Example 1: Case of centrifugal separation of oil-water separation system]

High calcium An extract was prepared by dissolving a variety of calcium extractants in the amount of four times the molar amount of calcium contained in the crude oil in the third distilled water. To the blender, 60 g of high-calcium crude oil and 20 g of the extract were mixed, followed by stirring at 90 ° C and 7200 rpm for 10 minutes. After completion of the reaction, the calcium compound removal step was carried out at 3500 rpm for 24 hours using a centrifuge.

After the centrifugation, the layer separation was performed between the oil layer and the aqueous phase of the high-calcium crude oil. The oil layer corresponding to the supernatant was separated and subjected to ICP analysis to analyze the residual calcium concentration. 1.

[Table 1]

From the results shown in Table 1, it was confirmed that when 2-oxopropanal was used as the calcium component extracting agent, the calcium component was removed from the high calcium crude oil at a much higher efficiency than other conventional extractants.

[Example 2: Separation of emulsion removal method by gravity and density difference]

High calcium crude oil and water were mixed at a volume ratio of 70:30, and then mixed with a blender for 20 seconds at medium intensity to produce an emulsion. After that, various calcium extractants and 100 ppm of calcium extract corresponding to twice the number of moles of calcium contained in high-calcium crude oil were added, and then mixed in a medium-intensity with a blender for another 20 seconds. After mixing, the mixture was placed in a vial, the stopper was closed, and the mixture was kept at 80 ° C for 1 hour. One hour later, an upper layer was obtained and the calcium concentration was measured using ICP-AES. The results are shown in Table 2 below.

[Table 2]

From the results shown in Table 2, it was confirmed that when 2-oxopropanal was used as the extracting agent of calcium component, the calcium component was removed from the high calcium crude oil at a much higher efficiency than other conventional extracting agents.

[Example 3: Isolation by electrodeposition method]

Washing water containing 2-oxopropanal corresponding to twice the number of moles of calcium contained in the high-calcium crude oil preheated to 90 ° C was added at a volume ratio of 90:10, and 1000 ppm of After adding a demulsifier, the emulsion was mixed with a blender for 10 minutes at a strong intensity. After mixing, the mixture was placed in a dedicated vial of an electric desalter in a batch type, and 8000 V of electricity was supplied at 87 캜 for 30 minutes. After the experiment, the upper layer was obtained, and the calcium concentration was measured using ICP-AES. The calcium removal rate was 92%.

It is to be understood that the present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (10)

A first step of adding an extraction agent comprising 2-oxopropanal to a hydrocarbon oil fraction to prepare a mixture;
A second step of reacting 2-oxopropanal with a hydrocarbon oil to convert a fat-soluble calcium compound into a water-soluble calcium compound; And
And a third step of removing the water-soluble calcium compound. 2. The method according to claim 1, wherein, in the first step,
Characterized in that the extracting agent is added in an amount of 0.1 to 100 times (based on the molar ratio) of the calcium content contained in the hydrocarbon oil fraction. 2. The method according to claim 1, wherein, in the first step,
Characterized in that the extracting agent is added in the solid phase or in the form of a mixed solution which is dissolved in water or an organic solvent. The method of claim 3,
When the extractant is added in solid phase,
≪ / RTI > and stirring at 0 to < RTI ID = 0.0 > 350 C < / RTI > to form a homogeneous mixture. The method of claim 3,
When the extractant is added in the form of a mixture of water and organic solvent,
≪ / RTI > and stirring at 0 to < RTI ID = 0.0 > 350 C < / RTI > to form a homogeneous mixture. 2. The method of claim 1,
≪ / RTI > is carried out at 0 to < RTI ID = 0.0 > 350 C. < / RTI > 2. The method according to claim 1,
A method of removing calcium in a hydrocarbon oil, characterized in that the water-soluble calcium compound is removed using gravity. 2. The method according to claim 1,
A method for removing calcium in a hydrocarbon oil, characterized in that the water-soluble calcium compound is removed using centrifugal force. 2. The method according to claim 1,
A method for removing calcium in a hydrocarbon oil, characterized in that the water-soluble calcium compound is removed using electric desalting or electric coalescence using an electric field. The method of claim 1,
Crude oil, Bio oil, Bio diesel, Tight oil, Shale oil, Oil sand, Liquefied coal oil, Tar sand, Pressure gauge Wherein the at least one gas is at least one selected from the group consisting of AR, Atmosphere residue, VR, Vaccum residue and hydrocarbon residual oil.

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